Highly radiation-sensitive telomerized polyesters



United States Patent 3,455,801 HIGHLY RADIATION-SENSITIVE TELOMERIZEDPOLYESTERS Gaetano F. DAlelio, South Bend, Ind., assignor, by mesneassignments to PPG Industries, Inc., a corporation of Pennsylvania N0Drawing. Filed Mar. 2, 1966, Ser. No. 531,024 Int. Cl. C08f 3/04 US. Cl.204159.19 9 Claims ABSTRACT OF THE DISCLOSURE Telomerized diacrylylpolyesters are obtained by reacting dicarboxylic acids with polyhydricalcohols having end groups capped by acrylic and methacrylic groups.These polyesters have the formula l, oHFo-o00R'0[ooRo00R'0]n0Oo=oH,where n is 1 to 14, R is a single valence bond or a divalent unsaturatedaliphatic hydrocarbon radical; R is a divalent aliphatic hydrocarbonradical and R" is hydrogen or methyl. These polyesters cure whensubjected to relatively low doses of ionizing radiation.

This invention in general deals with radiation-sensitive polymers.Particularly it concerns viscous, soluble, flowable, relatively lowmolecular weight polymers, known as oligomers, which, when subjected toionizing radiation become insoluble and infusible. More specifically, itdeals with telomerized polyesters which, on irradiation, convert tothree-dimensional crosslinked, insoluble, infusible polymers atrelatively low doses of ionizing radiation.

The telomerized polyesters used in the practice of this invention arelinear polyesters which are derived from the condensation of unsaturatedaliphatic, including cycloaliphatic, polycarboxylic acids with saturatedor unsaturated aliphatic, including cycloaliphatic, polyhydric alcoholswhose end groups are capped by the highly radiation-sensitive acrylylgroup,

B;'II OHFG-COO The simplest telomerized polyesters used in the practiceof this invention are those prepared from the reaction of one mole of anunsaturated aliphatic dicarboxylic acid, R(COOH) two moles of a diol,R(OH) and two moles of an acrylic acid,

RI! CH3=-COOH and have the general formula,

CHg=C-COOROOCROOOR'OOC=CH2 RI! RI! for example,

CH2=CHCOOCHzCHzOOGCH=CEOOCH2CH2OOCCH=CHI and In these formulas, Rrepresents a divalent unsaturated aliphatic, including cycloaliphatic,hydrocarbon radical having 2-10 carbon atoms; R is a divalent saturatedor unsaturated aliphatic (including cycloaliphatic) hydrocarbon radicalhaving 1-10 carbon atoms; and R is hydrogen or CH 3,455,801 PatentedJuly 15, 1969 Instead of the free acids, R(COOH) and CH ==CHCOOHsuitable derivatives such as their anhydrides, acid chlorides, 0r omegahydroxyalkyl esters may be used in the synthesis of these polyesters,and also instead of the diols, R(OH) the corresponding alkylene oxides,

RlllclCHR/II can, when available, also be used, wherein R' is H or analkyl group containing 1 to 10 carbon atoms.

Telomerized polyesters with a greater number of repeating segments, andtherefore of higher molecular weight than the simplest polyesters, areprepared by increasing the ratio of the n moles of dicarboxylic acid andthe n+1 moles of the diol to the 2 moles of acrylic acid to maintain themolar ratio of diacidzdiolzacrylic at n:(m+l) :2. Thus it may be seenthat the simplest polyester is obtained with one mole of diacid; twomoles of diol and two moles of acrylic acid. When the value of n isincreased for the dicarboxylic acid to 2, the value for the diol becomes3 and that for the acrylic function remains constant at 2.

In the case where n equal 1, the synthesis of these telomerizedoligomers can be accomplished by any or all of the following reactions,since it is immaterial in which order the reactants are combined. Theconditions used are those appropriate for the normal reactions ofalcohols with acids, anhydrides, and acid halides for the formation ofesters, and also those normally used, for the reaction of the glycidylgroup with the acids.

R!!! RI! I i I R(COOH): HOCHCH1OOOC=CHz R RI]! R!!! RI! I I I ICHFCOOOCHzOHOOCRCOOCHCH;OOCC=CH: (Eq. 10)

R(OO) O alt/(OH);

RI! R!!! R!!! RI! I I I CHF-COOCHCHgOOCRCOOCHzCHOOC-C=CH2 u- Oligomersin which the value of n is larger than 1 are readily prepared by thesame reactions as given hereinabove by simply changing the ratio of thedicarboxylic acid to the desired value of n and that of the diol to n+1while maintaining the molar quantity of the acrylic moiety at 2, thusnR(COH) (n+l)R'(OH):

Accordingly the radiation-sensitive telomerized polyesters useful in thepractice of this invention have the formula RI! R I ICH2=CCOOR'0[OCRCOORO]nOCC=CHz wherein n represents a numerical value of1 to 14; R

4 2,7-dihydroxy-n-hexene-4, 2,7-dihydroxy-2,7-dimethyl-nhexene-4,2-ethylhexanediol-1,3, etc. Alkylene oxides can also be used to givecorresponding glycol derivatives, such as propylene oxide, ethyleneoxide, 2,3-butylene oxide, etc.

Some illustrative examples of the various acids which can be used inpreparing the telomerized polyesters used in the practice of thisinvention are maleic, fumaric, itaconic, citraconic, mesaconic,acetylene dicarboxylic, aconitic, alpha-methyl-itaconic,alpha,alphadimethyl-itaconic, 1,2 tetrahydrophthalic, 1,3tetrahydrophthalic, 1,4-tetrahydrophthalic, trans-1,4-cyclohexene- 15dicarboxylic acids, etc. For the purpose of this invention,

polyesters are highly responsive to ionizing radiation, and

in fact, substitution of any of the aliphatic polycarboxylic acids byaromatic carboxylic acids or substitution of the aliphatic polyhydricalcohol by aromatic alcohols, decreases the response to ionizingirradiation to such a point that they are not economically feasible.

As an example, the dimethacrylyl telomerized polyethylene maleate,

0H; CH

crosslinks at about 2 megarads, Whereas the corresponding phthalylderivative,

I I CH2=C-C OIO CH OH O O C CeHlCOLO CHzCHgO O CC=CH5,

and the corresponding xyxyl derivative,

CH3 CH3 represents a divalent unsaturated aliphatic (includingcycloaliphatic) hydrocarbon radical having 2-10 carbon atoms; and Rrepresents a divalent aliphatic hydrocarbon radical, (saturated orunsaturated and including cycloaliphatic) containing 210 carbon atoms;and R" represents hydrogen or -CH;;. In other words,

represents the dicarboxylic radicals derived from maleic, fumaric,itaconic, citraconic acids, etc.

Depending on the nature of R, R' and R" the viscosity of thesetelomerized polyesters increases from about 100 to 9000 centistokes at20 C. as the value of n increases from 1 to 14. Also depending on thevalues of n, R and R", the molecular Weight of these telomerized esterswill vary from about 275 for the lowest One at a value of n=1 to about8800 for n equal to 14 when the diacid is decenedicanboxylie acid andthe diol is dodecanediol.

Some illustrative examples of the various HOR--OH alcohols which can beused in synthesizing the telomerized polyesters used in this inventionare ethylene glycol, trimethylene glycol, tetramethylene glycol,2,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4dihydroxy-2-ethylbutane,1,6 dihydroxyhexane, 1,8 dihydroxyoctane, 2,10 dihydroxydecane,1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane,2,2-diethyl-propanediol, 1,3, 2,2-dimethylpropanediol,1,3,3-methylpentanediol, 1,4, 2,2-diethylbutanediol 1,3, 4,5dihydroxynonane, pentamethylene glycol, heptamethylene glycol,nonamethylene glycol, decamethylene glycol, diethylene glycol,triethylene glycol,

propylene glycol, dipropylene glycol, butene-2-diol-1,4,

both require 12 and 14 megarads respectively, to become insoluble andinfusible.

This difference is surprising particularly because these threetelomerized esters all cure with radical initiators such as with 1%benzoyl peroxide in about to seconds at C., and with redox systems ofcobalt acetate and tertiary butyl hydroperoxide in three to three andone-half hours at room temperature. This difference is due apparently tothe fact that aromatic ring compounds such as phenyl, naphthyl and thelike are energy sinks for irradiation.

It will be noted too that the aliphatic hydrocarbon structures in thepolycarboxylic and polyhydric alcohol segments are unsaturated. This isfor the purpose of imparting rigidity to the irradiated products. Whilethe unsaturation in the acrylyl groups at the ends of the telomerizeddicaryl polyester is more easily available for crosslinking and insuresmore immediate and more easily attained crosslinking, the unsaturationprovided along the linear chain of the telomerized polyester by virtueof the unsaturation in the unsaturated dicarboxylic acid groups permitsa greater number of crosslinkages in a polymer molecule and therebyimparts a more rigid character to the resultant irradiated polyester.

The term irradiation, as used herein, means high energy radiation and/orthe secondary energies resulting from conversion of this electron orother particle energy to neutron or gamma radiation, said energies beingat least equivalent to about 100,000 electron volts. While various typesof irradiation are suitable for this purpose, such as X-ray and gammaand beta-rays, the radiation produced by accelerated high energyelectrons has been found to be very conveniently and economicallyapplicable and to give very satisfactory results. However, regardless ofthe type of irradiation and the type of equipment used for itsgeneration or application, the use thereof in the practice of theinvention as described herein is contemplated as falling within thescope of this invention so long as the ionization radiation isequivalent to about 100,000 electron volts.

While there is no upper limit to the electron energy that can be soapplied advantageously, the efiects desired in the practice of thisinvention can be accomplished without having to go above about20,000,000 electron volts. Generally, the higher the electron energyused, the greater is the depth of penetration into the massive structureof the materials to be treated, and the shorter is the time of exposurerequired to accomplish the desired result. For other types ofirradiation, such as gamma and X-rays, energy systems equivalent to theabove range of electron volts are desirable.

It is intended that the term irradiation includes what has been referredto in the prior art as ionizing radiation which has been defined asradiation possessing an energy at least suflicient to produce ions or tobreak chemical bonds and thus includes also radiations such as ionizingparticle radiation as well as radiations of the type termed ionizingelectromagnetic radiation.

The term ionizing particle radiation has been used to designate theemission of electrons or highly accelerated nuclear particles such asprotons, neutrons, alphaparticles, deuterons, beta-particles, or theiranalogs, directed in such a way that the particle is projected into themass to be irradiated. Charged particles can be accelerated by the aidof voltage gradients by such devices as accelerators with resonancechambers, Van der Graaif generators, betatrons, synchrotons, cyclotrons,etc. Neutron radiation can be produced by bombarding a selected lightmetal such as beryllium with positive particles of high energy. Particleradiations can also be obtained by the used of an atomic pile,radioactive isotopes or other natural or synthetic radioactivematerials.

Ionizing electromagnetic irradiation is produced when a metallic target,such as tungsten, is bombarded with electrons of suitable energy. Thisenergy is conferred to the electrons by potential accelerators of over0.1 million electron volts (mev.). In addition to radiations of thistype, commonly called X-ray, an ionizing electromagnetic radiationsuitable for the practice of this invention can be obtained by means ofa nuclear reactor (pile) or by the use of natural or syntheticradioactive material, for example, cobalt 60.

Various types of high power electron linear accelerators arecommercially available, for example, the Arco type travelling waveaccelerator, model Mark 1, operating at 3 to million electron volts,such as supplied by High Voltage Engineering Corporation, Burlington,Mass, or other types of accelerators as described in United StatesPatent No. 2,763,609 and in British Patent No. 762,953 are satisfactoryfor the practice of this invention.

In the following examples, the radiation doses are reported in megarads,which represent 1,000,000 rads. A rad is defined as the unit of absorbeddose and is equal to 100 ergs per gram.

Many monomers as well as polymers have been subjected to ionizingradiation to convert them to improved or modified products. However,irradiation processes have been primarily of scientific interest andvery little use of such irradiation polymer processes has been madeindustrially. This is primarily due to economic factors because of thecost of the ionizing radiation delivered to the system to be treated.For example, the well-known low-cost polyester systems which consist ofa mixture of about equal parts by weight of styrene monomer and anunsaturated alkyd resin prepared from maleic or fumaric anhydride,phthalic anhydride and ethylene glycol or diethylene glycol can be moreeconomically polymerized by free radical initiators than by ionizingradiation which requires about 25 to 40 megarads, depending on theformulation.

Such systems can be improved somewhat, however, by elimination ofphthalic anhydride in the formulation of the polyester and substitutingthe higher cost monomeric acrylic esters for the styrene. Even in suchsystems, the economic factors are unfavorable not only because of themuch higher cost of the mixture but because of the high volatility ofthe acrylic or methacrylic esters used. Even in such cases theirradiation dose required is of the order of 18 to 20 megarads and thesystems are highly inhibited by oxygen. The addition of substances suchas acetone or methyl ethyl ketone can reduce the required dose to 9 to12 megarads. Even then the products possess the undesirable odor ofunpolyme rized acrylic monomer.

In contrast, by the use of the acrylyl telomerized polyesters used inthe practice of this invention and described hereinabove, crosslinked,insoluble, infusible polymers can be prepared readily by subjecting thepolyesters to ionizing radiation in doses of less than 8 megarads and insome cases to doses of 0.5 megarad or less, generally preferably atleast about 1 megarad. Irradiation dosages in this range are economical.

Furthermore, the acrylyl components in these telomerized polyesters arelocated at the ends of the polyester chains Where they can moreeffectively crosslink. More important, the acrylyl components comprise aminor portion of the composition, and ar particularly economical whenthe value of n in these telomerized polyesters is at least 2. Inaddition, because the molecular Weight of the telomerized polyester ismuch higher than a corresponding simple monomer such as methylmethacrylate or ethyl acrylate, it can function in a single moleculeboth as monomer and as polymer.

This property of crosslinking at economical radiation doses ismaintained when these telomerized polyesters are admixed withunsaturated alkyd resins alone or in the presence of other polymersprovided the unsaturated alkyd resin and the other polymers are of thenonaromatic type, that is, they are free of aromatic rings which act asenergy sinks and retard the crosslinking reaction. One of the advantagesof these diacrylyl polyesters is their compatibility with various typesof resins, particularly polyester or alkyd types.

A few illustrative examples of suitable polymers which may be dissolvedin or mixed with the telomerized polyesters of this invention along withthe unsaturated alkyd resins are the nonaromatic type polymers such aspolyvinyl acetate, polyethyl acrylate, polymethyl methacrylate,cellulose acetate, cellulose butyrate, ethyl cellulose, polyethyleneadipate, polyethylene azeleate, polydecamethylene succinate,polydecamethylene sebacate, etc. The telomerized polyesters are alsocompatible with polyvinyl chloride, particularly upon the application ofmoderate heat. I

The telomerized polyesters of this invention are particularly useful ascoating compositions on all types of substrates, including cellulose inits various forms, such .as paper, wood, paper board, wood board, woodpulp, regenerated cellulose in film or fiber form, laminates of varioustypes including those prepared from fibrous fillers bonded with urea,melamine, epoxy and polyester resins, plaster board, concrete in itsvarious forms such as slabs, blocks and the like. They may also be usedas impregnants for porous bodies such as the compositions hereinabovenamed, as Well as for synthetic and natural sponges, etc. Particularlydo they find use as bonding agents and adhesives for solid, porous andfoamed bodies. They can be used alone or admixed with each other or withother copolymerizable monomers, unsaturated or saturated polymers, inthe absence or presence of dyes, pigments,

plasticizers. For coating, impregnating or adhesive compositions wherethe presence of small amounts of solvent in the cured composition is notobjectionable they can be mixed with volatile or nonvolatile solvents ofa nonaromatic nature best suited to the particular application. Theproducts resulting from the irradiation of the telomerized polyesters ofthis invention can vary from soft flexible bodies to hard rigid masses.

The telomerized radiation-sensitive polyesters of this invention areparticularly useful in the preparation of copolymers with unsaturatedalkyd resins. In carrying this portion of the invention into effect, anesterification product of a polyhydric alcohol and an alpha, beta,unsaturated polycarboxylic acid is first prepared in accordance withtechniques now well known to those skilled in the alkyd resin art.

Any aliphatic polyhydric alcohol containing at least two esterifiablealiphatic hydroxy groups, or mixtures of such alcohols, can be used inpreparing the unsaturated alkyl resins. Examples of such polyhydricalcohols are ethylene glycol, di-, tri-, and tetraethylene glycols,thiodiglycol, glycerine, pentaerythritol, 1,4 dihydroxy-butene- 2,dimethylol cyclohexane, dihydroxycyclohexane, etc. Any nonaromaticalpha-unsaturated, alpha,'beta-polycarboxylic acid, or mixtures of suchacids, can be reacted with the polyhydric alcohol or alcohols to 'formthe unsaturated alkyd resin. Examples of such polycarboxylic acids aremaleic, fumaric, citraconic, mesaconic, acetylene dicarboxylic,aconitric, cyclohexedicarboxylic, etc., itaconic and its homologues, as,for instance, alpha methyl itaconic acid, alpha,alpha-dimethyl itaconicacid, etc. Anhydrides of these polycarboxylic acids can also beemployed.

In some cases, instead of using an unmodified, unsaturated alkyl resin,an unsaturated alkyd resin can be used which has been internallymodified by replacing a part, say up to about 75 mole percent, of theunsaturated polycarboxylic acid with saturated aliphatic polycarboxylicacids, such as succinic, adipic, glutaric, pimelic, sebacic, azelaic,suberic, tricarballylic, etc.

Anhydrides of these acids, if available, can also be used. The termpolycarboxylic acid as used generally herein is intended to include theanhydrides of the acids.

The esterification products of polyhydric alcohols with ethylenicpolycarboxylic acids, or with aliphatic polycarboxylic acids, can befurther modified by introducing as a reactant in the preparation of thealkyd resin, a monesten'fiable compound or compounds, more particularlya saturated or unsaturated rated monocarboxylic acid, or mixturethereof, or both such estirifiable monohydroxy Organic compounds as wellas by the use of hydroacids.

Examples of nonaromatic monohydric alcohols which can be used asmodifiers of the alkyd resin are propyl, isopropyl, butyl, isobutyl,amyl, isoamyl, hexyl, octyl, decyl, dodecyl, tetradecyl, cetyl,octadecyl, cyclohexyl, cyclopentyl, etc. The use of methyl and ethylalcohol is not precluded, but in general these alcohols are less satisfactory because of their lower boiling points. As monobasic acids therecan be used, for example, the unsubstituted saturated and unsaturatednormal or isomeric monocarboxylic acids containing only one esterifiablegroup, such as acetic, propionic, butyric to stearic, inclusive,hexahydrobenzoic, hexahydrotoluic, furoic acids, etc.

The monoesterifiable compounds can be introduced into the esterificationbefore, during, or after the esterification of the polyhydric .alcoholwith the polycarboxylic acid under conditions that promoteinteresterification of the monoesterifiable compound with theincompletely esterified polyhydric alcoholpolycarboxylic acid product.That is, the monoesterifiable compound is introduced into the reactionmass before all of the acid groups of the polyhydric acid, or all of thealcohol groups of the polyhydric alcohol have been esterified.

The term unsaturated nonaromatic alkyd resins, as

used generally herein and in the appended claims, is intended to includewithin its meaning both unmodified esterification products of anonaromatic polyhydric alcohol with a nonaromatic alpha-unsaturated,alpha, beta-polycarboxylic acid and esterification products of thesecomponents which have been modified, for example, as briefly describedhereinabove. An alternate term is unsaturated aliphatic alkyd resins(including cycloaliphatic types).

To achieve copolymerization of the unsaturated alkyd resin with thetelomerized polyesters of this invention, a solution or mixture of theunsaturated alkyd resin in the telomerized polyesters is first elfected.Copolymerization of the components of the mixture is achieved rapidlyand advantageously by ionizing radiation, such as by atomic radiationfrom a reactor, or from cobalt 60, or by means of high energy electronsgenerated by an electron linear accelerator.

Typical examples of unsaturated alkyd resins are: ALKYD RESIN AETHYLENEGLYCOL ITACONATE Parts (by wt.) Ethylene glycol 23 Itaconic acid 52 Thecomponents are mixed and slowly heated in the course of one hour fromroom temperature to C., in an inert nitrogen atmosphere, and held atthis temperature for three to five hours.

ALKYD RESIN B-ETHYLENE GLYCOL MALEATE ALKYD RESIN CACETIC ACID-MODIFIEDDIETHYLENE GLYCOL MALEATE Parts (by wt.) Diethylene glycol 106 Maleicanhydride 88 Acetic anhydride 10 The ingredients are mixed together andrefluxed for one hour in an inert atmosphere of nitrogen after which thereaction mixture is brought to 190 C., which temperature is maintainedfor four to six hours.

It will be understood, of course, that this invention is not limited tothe use of the specific unsaturated alkyd resins mentioned above andthat a broad modification of the nature of the copolymer is possible byusing other unsaturated aliphatic alkyd resins or mixtures of suchresins. As illustrative examples of other unsaturated alkyd resins, thefollowing esterification products can be used, as illustrated in alkydresins D and I. Aromatic alkyd resin J is included for comparison.

Ethylene glycol (20).

H Maleic anhydride (29.4).

Succinic acid 3.3). Diethylene glycol (30.6).

I Maleic anhydride (17.6).

Itaconic acid (15.6). Diethylene glycol (30.3).

I Maleic anhydride (13.2).

Phthalic anhydride (21.7).

In many cases, instead of polymerizing a single telomenzed polyesterwith a single unsaturated alkyd resin, mixtures can be used of two ormore telomerized polyesters with a single unsaturated aliphatic alkydresin, or a single telomerized polyester with two or more unsaturatedaliphatic alkyd resins, or a mixture of two or more telomerizedpolyester-s with two or more unsaturated aliphatic alkyd resins. Inconjunction with the alkyd resins, comonomers can be used which arecopolymerizable with the telomerized polyester or with the unsaturatedalkyd resins, or with both, for example, one or more telomerizedpolyesters can be used with one or more unsaturated aliphatic alkydresins together with methyl methacrylates.

In addition to, or in lieu of the methyl methacrylate, other comonomersor mixtures of comonom rs can be used, for example, the vinyl esters,that is, vinyl acetate, and the vinyl esters of saturated andunsaturated, and aliphatic, monobasic and polybasic acids, and morespecifically the vinyl esters of the following acids: propionic,isobutyric, valeric, caprylic, capric, oleic, stearic, acrylic,methacrylic, crotonic, oxalic, malonic, succinic, glutaric, adipic,suberic, azelaic, maleic, fumaric, itaconic, mesaconic,hexahydrobenzoic, citric, trimesic, etc., as well as the correspondingallyl, methallyl, etc., esters of the aforementioned acids.

Other suitable comonomers are the acrylic and alkacrylic acids and theirderivatives, such as their esters, amides and corresponding nitriles,for example, acrylic acid, methyl acrylate, butyl acrylate, allylacrylate, ethylene glycol diacrylate, acrylonitrile, methacrylonitrile,methacrylic acid, methyl methacrylate, etc.; the itaconic acidmonoesters and diesters, such as the methyl, ethyl, allyl, dimethallyl,the maleic and fumaric acid monoesters, diesters and their amide andnitrile compounds, such as ethyl allyl maleate, fumaryl dinitrile,dimethallyl fumarate, etc.; the ethers, such as methallyl allyl ether,vinyl allyl ether, vinyl methallyl ether, allyl crotyl ether, vinylcrotyl ether; cyanuric acid derivatives such as diallyl cyanurate,triallyl cyanurate, trivinyl cyanurate, or in general, triazinecompounds having at least one polymerizable or copolymerizableunsaturated group attached directly or indirectly to the triazine ring,as well as the partial, soluble or fusible polymers of the hereinabovelisted monomers, etc.

The modified unsaturated aliphatic alkyd resins of this invention can beused alone or with fillers, dyes, pigments, opacifiers, lubricants,plasticizers, natural and synthetic resins, or other modifying bodiesin, for example, casting, molding, laminating, coating applications, andas adhesives, impregnants, and protective coatings.

In coating, impregnating and similar applications, the mixed monomericor partially copolymerized materials, without added solvent can beapplied to the object to be treated and polymerized, with or without theapplication of heat and pressure, to form the final insoluble polymericcomposition in situ. These new synthetic materials can be used asimpregnants for many porous bodies, such as cork, pottery, felts, orfabricated bodies with interstices, such as the windings of electricalcoils, netted fibers, interwoven fibrous cotton or glass materials, etc.They can also be used for the production of wire coatings and windingtapes, and for protectively coating impervious articles, such as metals,or for coating and impregnating articles such as paper, wood, cloth,glass fibers in felted, woven or other form, concrete, linoleum,synthetic boards, etc. These new synthetic materials can also beemployed in making laminated fibrous sheet materials whereinsuperimposed layers of cloth, paper, glass fabrics or mats, etc., arefirmly bonded together with these new compositions. Also, these newmixtures comprising at least one telomerized polyester of this inventionand at least one unsaturated aliphatic alkyd resin, with or withoutmodifying agents, can be cast under pressure while being irradiated.

In preparing the interpolymerization products of the unsaturatedaliphatic alkyd resin and the telomerized polyester, the unsaturatedalkyd resin can constitute as much as 98 or 99 percent by weight of thewhole. In other cases the telomerized polyester alone, or admixed withaliphatic comonomers or modifiers, can constitute as much as 98 to 99percent by weight of the whole.

In general, the proportions of the components used in a particularformulation will depend upon the particular properties desired in theinterpolymer. For most applications, it is preferred to use 30 topercent of the unsaturated aliphatic alkyd resin and from 10 to 70percent of the telomerized polyester, since within these rangesinterpolymers best adapted for most commercial applications can beproduced.

Within these ranges the new interpolymers have a wide range ofproperties. For example, depending upon the.

particular telomerized polyester or mixture of telomerized polyestersused with the particular unsaturated aliphatic alkyd resin theparticular properties thereof, the conditions of polymerization, such asthe temperature, pressure, presence or absence of additives, etc., theirradiation dose, and the extent of polymerization, they can vary in thedegree of hardness, rigidity and resistance to solvents.

In the intermediate stages of copolymerization, some form fluidcompositions of varying viscosities and may be so used. For coating orimpregnating applications where the presence of a small amount ofsolvent in the cured composition is not objectionable, the mixedstartting component can be diluted with volatile or non-volatilesolvents or diluents best suited for the particular service application,and then can be polymerized after the application of the solution to theparticular article to be coated or impregnated, or impregnated andcoated. By suitable selection of the starting material and theconditions of the interpolymerization, interpolymers can be obtained inan insoluble, infusible state practically resistant to the destructiveeffect of other chemical bodies, such as acids, bases, salts, solvents,swelling agents, and the like.

When it is desired to modify the properties. of the polymers of thetelomerized polyesters of this inven tion, this can be accomplished bycopolymerizing a mixture comprising at least one telomerized polyesterwith at least one copolymerizable unsaturated ethylenic, or acetylenichydrocarbon radical, more particularly, a CH =C radical, such as vinyl,allyl, methallyl, vinylidene, etc., or with a copolymerizable compoundcontaining a CH=CH or a CH=C or a C==C grouping, for example, as invinylidene fluoride, vinylidene cyanide, vinyl propionate, maleicanhydride, or its esters and amides, methyl maleic anhydride,tetrafluoroethylene, etc.

Additional examples of copolymerizable comonomers are monomeric orpartially polymerized vinyl esters, such as the acetate, propionate,etc.; vinyl ketones, methvinyl ketones, olefinic nitriles, such asacrylonitrile, methacrylonitrile, fumaryl nitrile,beta-cyanoethylacrylate, acrylic and methacrylic esters, for example,methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, octylmethacrylate, glycol dimethacrylate, allyl methacrylate, etc.; itaconicesters, for example, dimethyl itaconate, diethyl itaconate, diallylitaconate; olefinic amides, for example, acrylamide, itaconamide, themaleic monoand diamides, and the corresponding imides, etc.; the vinylethers, for example, vinyl butyl ether, vinyl isobutyl ether, vinylcyclohexyl ether, the dienes, etc., for example, butadiene, isoprene,dimethyl butadiene, etc.

In preparing copolymers of the telomerized polyesters with otherpolymerizable comonomers such as methyl methacrylate, acrylonitrile, andthe like, the telomerized polyesters can constitute as little as 0.1percent by weight of the whole, whereas in other cases, the telomerizedpolyesters alone can constitute as much as 98 to 99 percent of thewhole. As in the case of the copolymers with unsaturated aliphatic alkydresins, the proportion of the components in a particular formulationwill depend upon the particular comonomers used and the particulartelomerized oligomer I (a) CHz=( lC O CHaCHO O C CH=OHCO O CHrCHzO 0 CCH=CHCO O ([lHCHzO O CC=OH2 properties desired in the copolymer. Thepolymers and copolymers can be prepared most readily by ionizing whichis a slightly viscous, light-colored oily product. When an equivalentamount of 2-hydroxypropylene acetate is substituted for the methacrylatethere is obtained a viscous product having the formula (IJ') CH C O OCHz(]JHOO C CH=CHC O O CHzCHgO O C CH=GHCO O OHCHgO O OCH;

trated -by the following examples. These examples are intended merely toillustrate the invention and not in any sense to limit the manner inwhich the invention can be practiced. The parts and percentages recitedtherein and all through this specification, unless specifically providedotherwise, refer to parts by weight and percentages by weight.

Example I In a suitable reaction apparatus equipped with a stirrer,reflux condenser, inert gas inlet, heating mantle, and thermostaticcontrol for the reactor, are placed 28.8 parts Example II The procedureof Example I is repeated ten times using respectively instead of the28.8 parts of 2-hydroxypropyl methacrylate:

of 2-hydroxypropyl methacrylate, 20 parts of maleic (h) 39.0 parts Of1,4-hexahydroxylylidene glycol monoanhydride, and 0.25 part ofhydroquinone. The apparatus is first deoxygenated by sweeping drydeoxygenated nitrogen through the apparatus and thereafter allowing aslow stream of nitrogen to pass through during the acrylate. (i) 33.0parts of 1,4-cyclohexanediol acrylate. (i) 45.6 parts of1,10-decamethylene glycol acrylate.

There are obtained respectively l (a) CH2=CC O O CHaCHzO O C CH=CHO O OCHzCHaO O O OH=CHC O O CHzCHzO O C=OHa (b) CHz=CHC O O OHaOHaO O CCH=OHC O O CHzCHzO O C CH=CHO O O CHzOHaO O C OH=CH2 (c') CH=CHO O OCHaCHO O C CH==CHC O O OHaCHgO O C CH=OHC O O (EEC/H O O C OH=CHI (d')CHg=CHC O O CHBCHZCHflO O C CH=CHC 0 0 CHzCHaO 0 C CH=CHC O O CHgCHgCHaOO C CH=CH1 (3H5 CH ((5') CHz=CC O O CHzCHzCHgO O C CH=CHCO O CHzCHzO O CCH=CHC O 0 CHBCHQCHZOO C C=CH (f 2= C O O (CH2CH20)2O 0 C CH=CHC O OCHQCHQO O C CH=CHC O O (O CHzCHzhO O C CH=CH2 (3H3 CH3 (9') CH3=C-C O O(CH2CHQO)2O O C CH=CHC O O CH2CH2O 0 C CH=CHC O O (O CHaCHnhO 0 CiJ=OHsCH CH:

(h') ICHg=CHCOOCHg-CH CHCH200CCH=CHOOCH212 CHxC 3 CHzCHz (2")[CH:=CHCOOCH CHOOCCH=CHCOOCH2I3 (j) CH =CHO O O (CH2)ioO O C CH=CHC O OCHaCHgO O C OH=CHC O O (CHz)1uO O G CH=CH2 reaction. The mixture isheated to 125-130 C. for thirty minutes to give a quantitative yield of0 Example HI The procedure of Example I is repeated six times usingrespectively instead of the six parts of ethylene glycol:

(a) 9 parts of butylene glycol. C1211, (b) 17.4 parts of decamethyleneglycol. H00CCH=CHCOOCHCHQOOC C=OHI (c) 11.8 parts of hexamethyleneglycol.

(d) 7.6 parts of propylene glycol. (e) 11.6 parts of1,4-cyclohexanediol. (f) 14.4 parts of 1,4-hexahydroxylylidene glycol.

15.0 arts of trieth len l 1. Then six parts of ethylene glycol are addedand the (g) p y e gyco reaction continued for about four hours or untilthe acid There are obtained respectively CH; CH (6)H;=('1C00OH=OH000CH=oHGoo(oH,)mo0coH=oHOo0GHOH,00Ci:=oH,

(EH3 (3H3 CH; CH; (c)CHpCJ-COOCHQCHOOCCH=GHCOO(CH;)tOOOCH=CHCOOCHCH1OOCO=CH;

H3 (IE3 (IE3 0H, (d) CHGOOOGHnCHOOCCH=CHCOOCHCHzOOCCH=CHCOOCHCH,OOCC=CH;

3133 CH: CH; CH; CHOOCCH=CHCOOCH CHzCH: CH: (e') 0H2=(JO0ooH=CH0oooH=0Ho00C CHO0GCH=GHC00cHcH,00C-C=i3H:

(3H3 CH:CH1/ (IJH1 CH 011,011: CH: (1'') CHz=i3-COOCHzCHOOCCH=CHCOOCHgCCHOH,00C0H=OHo00CH0H1O0C-h=CHz (I311; CH:C 5H: CH; CH: (9') CHp-(J-COOCHCHOOCCH=CHCOO(CH:CH:O);OCCH=CHGOOCHCHzOOC-E=CH- I H3 ICH3 Example IV fortwenty minutes at 130 C. Then there is added 6 The procedure of ExampleI is repeated using respectively instead of the 20 parts of maleicanhydride:

(a) 22.5 parts of citraconic anhydride.

(b) 30.8 parts of 1,2-tetrahydrophthalic anhydride.

(c) 225 parts of itaconic anhydride. (d) 22.5 parts of mesaconicanhydride.

parts of ethylene glycol, 0.15 part of toluene sulfonic acid, and 100parts of toluene and the mixture refluxed until no more water ofcondensation is collected in the Dean- Stark trap. The mixture is thenneutralized with solid sodium bicarbonate, filtered and the tolueneremoved by distillation at 15 mm. pressure, leaving I CHF=C-CO O CHgCHzOO CCH=CHCO O CHQCHQO O C CH=OHCO OCHiCHzOO C-O=CH1 There are obtainedrespectively CH3 ((1') CHJCOOCHzCHOOCCH=CCOOCHQCHQOOCCH=CCOOCHCHzOOC-(E=CH1 H I CH3 CH1 CH; CH!

CH: CH; CH: CH, (1)) CHFC-COOCH:CHOO3=iJCOOCHzCHaOOCb=CCOOCHCHQOOC-C-CHI CH3 (6') CH COOCH3CHO0CCCHCOOCHgCHQOOCCCHiCOOCHCHzOOCiJ=CH CH3 Hz 3H3 CH3 ((1')CHFCOOCHzCHOOCC=CHCO0CH2CH2OOCC=CHCOOCHCHQOOCE=CHI CH3 CH3 3H3 Example VAll of the radiation-sensitive acrylyl terminated polyesters of ExamplesI to IV inclusive can be prepared by alternate procedures as illustratedin the following methods A and B for the synthesis of Method B.--Theprocedure of Example V is repeated with the exception of the order ofaddition of the reagents. The 20 parts of maleic anhydride and 6 partsof ethylene glycol are first reacted at 130 C., then the hydroquinone,the toluene, toluene sulfonic acid and the l l CH =CCO O CHzCHzO O CCH=GHCO 0 011101110 0 C OH=CHCO O CHzCHaO OCC=CH When the other reagentsused in Examples I, II, III and IV are reacted by methods A and B, thedesired products are also obtained.

Method A.'Ihe reactor of Example I is equipped with a Dean-Stark trap tocollect condensed water, and to the reactor is added 26 parts of2-hydroxyethyl methacrylate, 0.2 part of hydroquinone and 20 parts ofmaleic anhydride hydroxyethyl methacrylate are added and the reactioncontinued until no more water of condensation is collected, then thetoluene is removed by distillation, leaving the same product as that ofExample Ila and Example V-A.

Example VI To the Dean-Stark reactor of Example V-B there is and themixture reacted in an inert nitrogen atmosphere added 116 parts ofmaleic acid, 260 parts of hydroxyethyl methacrylate, 1 part of toluenesulfonic acid, 500 Example VIII parts of toluene, 1 part of hydroquinoneand the mixture In the reactor of Example I there is placed 26 partsrefluxed until 36 parts of water are collected in the trap. fhydroxygthyl methacrylate, 50 parts of carbon tetra- The toluenesulfonic acid is neutralized with calcium chloride, 05 part ofhydroquinone, '8 parts of sodium hydroxide, the Solution fi tered, andthe toluene removed 5 hydroxide dissolved in 50 parts of water, and tothe stirred by distillation at reduced pressure, leaving mixture isadded, at C. slowly over a period of one (a) CH CH3 (Ego-00wCHZCHiOOCCHICHflC 0110 oH,oH,000i)=oH, This product is related to theproduct of Example Ila, hour, 15.3 parts of fumaryl dichloride dissolvedin 50 which can be written as 1 parts of carbon tetrachloride. Thereaction mixture is then CH: CH3 CH JCO[O OHQCHQO 0 G CHaCHaCOhO CHQCHQOO CJ=CHz Example VII 15 washed four times with 100 parts of water, driedover anhydrous sodium sulfate, filtered, and the carbon tetrachlorideremoved from the reaction product by distillation at 15 mm. pressure,leaving as the product When 28.8 parts of 2-hydroxypropyl methacrylateare used in this procedure instead of 26 parts of hydroxyethylmethacrylate, there is obtained CH: (EH; (3113 (EH: CH:=-CO O CHzCH-O OC CH=CHCOO CHCHzO O C-C=CH1 The procedure of Example V1 is repeated anumber of times, but instead of using the 116 parts of maleic acid (1mol. weight) equivalent molar weights of the following acidsrespectively are used: 0 Example 1X 0 C O00H umaric) 3 To the reactor ofExample I is added 24 parts of ethyl- (b) H0OO(CH2)4CH=OH(CH2)4COOH eneglycol and 49 parts of succinic anhydride (or 58 parts (0) HOOCC=CHCOOHof succinic acid) and the mixture reacted at 180 C. for H3 six hours oruntil titration of a sample with 1 N sodium CH=CH hydroxide shows thatit is substantially H0 0 fl 0 0H HOOC(CH CO[OCH CH 0OCCH=CHCO] 0H (8) ZZZ Z The product is then transferred to the Dean-Stark reactor 11 ofExample V-B, to which is added 26 parts of 2-hydroxyethyl acrylate, 0.5part of toluene sulfonic acid, 150 U) CH=CH parts of toluene, 1 part ofhydroquinone, and the mixture H0CHCCH CH-CHCOOH refluxed until no morewater of condensation is collected CHZC 2 in the trap. The mixture isthen treated as in Example (0) H0000=0000H V 13, and there is isolatedthe product CHa CH3 CH; CH; 011,:(7-00 [0 CH OH OOCOH=CHC 0150CHZCHZOOCIC=CH:

and there is obtained CH; 011, (a) CHFC-CO 0 CHflCHiO 0 o CH=CHC 0 0011201120 0 C-( 3=CH1 CH; CH3 (1)) CHg-=(!'J-C O O CHICHIO O C(CH2)4CH=CH(CH1)4C O O CHzCHaO O C-C=CH;

CH3 CH3 (c) oHFo-o 0 o CHzCH O 0 o C=CHC 0 0 CHQCHzO o Ct 3=CHg Cm CH=CHCH3 ((1') GH= B-OOOCH2GH3OOCCH GHOCHzCHzOOC-(3=CH2 CHzC CH; CH: (e) OHJC O 0 0111011 0 0 C CHZC O O CHzCHzO 0 C&=CH (5H5 CH3 CH=CH CH3 (1'')CH:=C-C O O CHzCHaO O C CHzCH CHOHZC O O GHzG'HzO O G( 7=C.Ha

CHzC 3 CH: OH:

I (11') CHr--C O O CHzCHgO O C C=C C O O CHzCHgO O CC=CH1 a Ha Example Xis observed at higher dosages than megarads and crosslinking becomesevident at about 23 megarads for the samples of Example XI, and at aboutmegarads for the samples of Example XII. These show the effect of thearomatic nuclei on the radiation dose required.

The procedure of Example IX is used except that 54 parts of ethyleneglycol and 98 parts of maleic anhydride are used instead of 24 parts and49 parts respectively, and

there is obtained 5 ([3113 (3H3 (a)CHg=C-CO[OCHzCHzOOCOH=CHCO]mOCHzCH;OOCC=CH In a similar way by using 66parts of ethylene glycol Example XV and 118 parts of maleic anhydride,there is obtained The procedure of Example XIII is repeated seventeenwith 84 parts of ethylene glycol and 147 parts of maleic times usingrespectively the samples of Example II, a, b,

anhydride there is obtained c, d, e, f, g, h, i, j, and Example III, a,b, c, d, e,

(3H3 (3133 (c) CH -CCOO[OCHgOHzOOCCH=CHOO]15OCHzCH2OOCC=CHg By varyingthe above ratios there is also prepared f, g. Sample Ila and 11bcrosslink at between 1.35

CH3 CH3 Example XI 25 and 1.5 megarads, and all the others, with theexception of Sample IIIg' crosslink between 1.9 and 2.3 megarads, whileIIIg crosslinks at 2.8 megarads. The products are very hard.

The procedures of Examples IX and X are repeated using equivalentquantities of an aromatic dicarboxylic acid, phthalic anhydride, andappropriate multiples thereof, instead of the aliphatic dicarboxylicmaleic anhydride, Example XVI and there is obtained a series of productsof the general The producedure of Example XIII is repeated four formulatimes with samples of Experiment IV, a, b, c, d, and all of themcrosslink with radiation doses in the range of (IE3 (3H3 1.95 to 2.55megarads to give very hard products. oHFo-o o[o CHZC H2OOCCBH4C 01.0oH2oH2oooo=oH; Example XVII n=1 in sample a, All of the telomerizedpolyesters of Examples V to IX, n=5 in sample b, inclusive, areirradiated by the procedure of Example 11:10 in sample 0', XIII, and allcrosslink at irradiation doses of less than 3.2 11:12 in sample d.megarads.

Example XVIII Example XII The telomerized polyesters of Example X arecast into The Procedures of EFEamPIeS IX and e repeated glass vials byfirst heating them to 80 C. and then allowllsiflg equivalent quantifiesof all arematle dlaleehel P- ing them to cool to room temperature andexposed to the Xylyhdefle g y z e t z and P'P p ionizing radiation beamof a 0.450 mev. electron accelermlllfiples thereof, instead of ethyleneglycol, and there is ator. All of them become insoluble and infusible atthe obtained a series of products of the general formula foll i dosages;

Megarads E E Sample Xa', 11:10 4.2 CH2=CCO[O CHzCHzOO ofimo 01.0 CHCHgOOC-C=CH2 Sample Xb', :12 4,6 h Sample Xc', 12:15 6.8 W 16 SampleXd', "=14 5.2

n=1 in sample a, n: 5 in Sample Th1s data lndlcates that, a value of nof less than 15, that 71:10 in Sample C" is, of 14 or less represents aneconomical upper limit for H215 in sample these telomerized polyesters.This value of less than 15 can be obtained as an average value such asfor example,

EXAMPLE XIII by mixing equal portions by weight the sample of ExampleIX, in which n=5 and the sample of Example Xc' in which n=15. Such amixture crosslinks at a dosage of 3.7 megarads.

When a mixture of nine parts of the polymer of Example 11a and one partof the polymer of Example Xc' are mixed, irradiation crosslinking isobserved at 2.6 megarads.

A sample of liquid polyester, Ia, in a layer one-half inch thick isplaced in an aluminum cup and exposed, while open to air, to the beam ofa l-mev. Van der Graaif accelerator. An increase in the viscosity of thesample is observed at 0.8 megarad and at 1.7 megarads the sample becomescompletely crosslinked. When an identical sample is exposed to theelectron beam of an Arco Mark Example XIX I microwave linear acceleratoroperating at a beam energy Parts of 8 mev., the sample also becomesinsoluble and infusi- Alkyd resin A 80 ble at the same dosage,indicating that these telomerized Telomerizcd polyester, Example 20polyesters are dose-rate independent.

The alkyd resin A and the telomerized polyester are Example XIVthoroughly and uniformly mixed and subjected to ionizing radiation andconverted to an insoluble, infusible hard The samples of Example XI, a,b, c, d, and Example product at a dose of 3.15 megarads. XI, a, b, c,d', were irradiated by the procedure of Ex- Fillers such as wood flour,alpha cellulose, shredded ample XIII and no evidence of crosslinking isobserved cellulose derivatives, asbestos, paper, cloth, sand, silica,

at l, 2, 5, and 10 megarads. Some increase in viscosity calcium sulfate,etc., can be coated or impregnated with 19 the mixture and the masshardened by irradiation to produce formed articles of good appearanceand excellent physical properties and improved heat resistance.

To improve the heat resistance further the foregoing procedure ismodified using a higher ratio of telomerized polyester to theunsaturated alkyd as follows:

Parts Alkyd resin A 50 Telomerized polyester 50 and Alkyd resin A 75Telomerized polyester 2S Compositions of the kind illustrated in thisexample have the advantage that they do not contain radical initiatorsand can be stored for long periods of time, and still are readily curedwithout the addition of catalyst by the simple expedient of subjectingthem to irradiation.

Example XX The procedure of Example XIX is repeated except that insteadof alkyd resin A, there is used alkyd resin B and infusibility andinsolubility is obtained at 2.83.8 megarads of irradiation.

The compositions of Examples XIX and XX can be used as room temperature,low pressure laminating resins for the preparation of reinforcedlaminates from glass mats or fabrics.

It will be understood of course that this invention is not limited tothe interpolymerization of alkyd resins A and B with the telomerizedpolyester of Example Ia and that another acrylyl telomerized polyesteralone or in combination can be used, for example, the telomerizedpolyesters of Examples II to X, inclusive, can be used.

In contrast, when the aromatic containing telomerized polyesters ofExamples XI and XII are used, irradiation doses in excess of 18 megaradsare required to produce hard infusible polymers.

Similarly, high irradiation doses in excess of 16 megarads are requiredwhen the aromatic containing alkyd resin I is used with the acrylyltelomerized polyesters in contrast to the use of alkyd resin C, D, E, Hand I which become infusible and insoluble in the range of 3.8 to 4.0megarads.

The use of unsaturated alkyd resin G, which is an acrylyl terminatedunsaturated alkyd in admixtures with the acrylyl telomerized aliphatictype polyesters, for example, the polyesters of Examples I, II and IIIis particularly beneficial since in all cases crosslinking occurs withinthe range of 1.6 to 2.0 megarads.

Example XXI A smoothly sanded pineboard 12 inches by 36 inches and%-inch thick is coated on one surface with a mixture of equal parts ofpolyester of Example 11a and Example IX to produce a layer of polyester0.005-inch in thickness, and the board is progressed under the sweepingbeam of the linear accelerator to be given a uniform dose of 2.9megarads. The finished board has the appearance of a high glossvarnished lumber.

When the above polyester mixture is blended and milled with 60 parts oftitanium dioxide pigment (paint grade) and the pigmented polyesterapplied to wood, fiber board or concrete block, a porcelainized finishis obtained when the coating is irradiated.

Example XXII Fifty parts of the telomerized polyester of Example Ia isdiluted with parts of glycol dimethacrylate and a concrete panel Az-inchthick is impregnated with this solution and the panel irradiated to adosage of 3.0 megarads; a water-impervious panel is obtained.

20 Example XXIII A mixture of parts of exploded wood fibers of the typeused to prepare fiber board, 12 parts of the telomerized polyester ofExample X17, 1 part of zinc stearate and seven parts of linseed oil aremilled to uniformity, pressed into a board and given 4.3 megarads ofirradiation. There is obtained a well knit, hard board which is readilypaintable with either solvent type paints, or aqueous emulsion paints.

Example XXIV Four parts of the polymer of Example Xb' are added to 10parts of water containing 0.5% of sodium dioctyl sulfosuccinate as anemulsifying agent and the mixture emulsified in a colloidal mill. Theemulsion of the telomerized polyester is added to 50 parts of prepuifedpolystyrene beads mixed and the mixture tumbled until all the beads areuniformly coated. The water is then allowed to evaporate from the coatedfoamed beads which adhere slightly to each other. The coated foamedbeads are then placed in a container such as a cardboard box andirradiated to a dose of about 3.6 megarads. By this process there isobtained a foamed structure in which the beads are all bonded withinfusible bonds to each other, the shape of which conforms to the formof the container.

Example XXV A uniform mixture of 40 parts of the diacrylyl polyester ofExample I and 60 parts of a plastisol grade of poly vinylchloride havinga molecular weight of about 25,000 is prepared. This is melt extrudedinto pipe and given an irradiation dose of 3 megarads. Thepo1yvinylchloride is not degraded by this small dosage and the treatmentmakes the pipe insoluble and infusible so that it withstands hot water210 F. and hot saturated brine at 215 F. Without softening. It alsowithstands hot solutions of acetic acid, toluene, carbon tetrachloride,etc.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention and it is not intended to limit the invention tothe exact details shown above except as they are defined in thefollowing claims.

The invention claimed is:

1. A process for producing an improved polyester resin compositioncomprising the treatment of a highly radiation-sensitive telomerizeddiacrylyl polyester having the formula R represents divalent unsaturatedaliphatic hydrocarbon radical having 2-10 carbon atoms;

R represents a divalent aliphatic hydrocarbon radical having 210 carbonatoms;

R" is selected from the class consisting of hydrogen and methyl; and

n is an integer having a value of l-14; with at least about 0.5 megaradand no more than about 8 megarads of high energy ionizing radiationequivalent to at least 100,000 electron volts.

2. The process of claim 1 in which said diacrylyl polyester isintimately admixed with a copolymerizable monomer, said diacrylylpolyester comprising 1-99 percent by Weight of said copolymerizable massand said copolymerizable monomer comprising 99-1 percent by weight ofsaid copolymerizable mass.

3. The process of claim 1 in which said diacrylyl polyester is inintimate admixture with an unsaturated aliphatic alkyd resin, saiddiacrylyl polyester comprising 10-70 percent by weight of saidcopolymerizable mass and unsaturated aliphatic alkyd resin comprisingabout 30-90 percent of said copolymerizable mass.

21 22 4. The process of claim 1 in which said diacrylyl polywhereinester has the formula R represents a divalent unsaturated aliphatichydrocar- =bon radical having 2-10 carbon atoms; (1H3 $H; CHFC-C O OCHsCfHO O C CH=CHCO O CHaCHzO O C CH=CHC O OICHOH1O O C-C=OH:

CH3 CH3 5. The process of claim 1 in which said diacrylyl poly- Rrepresents a divalent aliphatic hydrocarbon radical ester has theformula having 2-10 carbon atoms;

CH; OH:

I I CHQ=CCOOCH2CHQO OCCH=CHCCHzCH2OOCCH=CHC0OCH:CH2OOCC=CH:

6. The process of claim 1 in which said diacrylyl polyi ester has thformula R" 1s selected from the class consisting of hydrogenCHFCHC00CH2CH2OOCCH=CHCOOCH2 and methyl; and

n is an-integer having a value of ll4;rwith at leastCHZOOCCHCHCOOCHZCHZOOCCHCHZ about 0.5 megarad of high energy ionizingradiation 7. The process of claim 1 in which said diacrylylpolyequivalent to at least 100,000 electron volts. ester has the formula$H3 (1H1 CHg=C-OO[OCH;CH;OOCCH=CHCO110OCH1CH2OOCC=CH2 8. The process ofclaim 1 in which said diacrylyl poly- References Cited ester has theformula UNITED STATES PATENTS CH; CH; 2,379,251 6/1945 Muskat et a1260485 ,=i c0ocmnoocc =c coocm 2 33 M Kraft 260-76 3,336,418 8/ 196-7Dill 260-884 g OTHER REFERENCES v g (IIH: 'y-Initiated Crosslinking ofUnsaturated Polyesters, W. Burlant and ,J. Hinsch, Journal of Polymerscience, E vol. 61, pp. 303309 (1962). CHFC-C o o omcno o o CH=CHC o 00E, Chemical Abstracts, vol. 54, p. 6204f.

9. A process for producing an improved polyester resin 35 AY LL A i icomposition comprising the treatment of a highly radiation-sensitivetelomerized diacrylyl polyester having the RICHARD TURER AsslstantExammer formula US. Cl. X.R.

f" 1 2602.5, 17, 17.4, 22, 40, 75, 485, 486, 861, 862; 117- oH,=c-oooR'o0cRc0oR'o],,oc- =CH: 161; 204-15916, 159.19, 159.22

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,455,801 July 15, 1969 Gaetano F. D'Alelio It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Column 13, at the end of formula (b) in Example IV,

"'CH should read =CH Signed and sealed this 18th day of November 1969.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Commissioher of Patents Attesting Officer

